CN106661262A

CN106661262A - Porous imide resin film production system, separator, and porous imide resin film production method

Info

Publication number: CN106661262A
Application number: CN201580033108.3A
Authority: CN
Inventors: 川村芳次; 水木秀行; 杉山真也
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2014-06-20
Filing date: 2015-06-16
Publication date: 2017-05-10
Anticipated expiration: 2035-06-16
Also published as: KR20170012341A; WO2015194546A1; CN106661262B; TW201600301A; JP6539655B2; TWI673154B; KR20180122042A; JPWO2015194546A1; KR102244104B1; KR101915698B1

Abstract

Provided are: a porous imide resin film production system with which it is possible to improve the production efficiency of a porous imide resin film; a separator; and a porous imide resin film production method. This system comprises an application unit (10) which applies a coating solution (first coating solution and second coating solution) containing polyamic acid, polyimide, polyamide-imide, or polyamide resin material and microparticles onto a carrier substrate to form an unfired film; a firing unit (20) which fires the unfired film peeled from the carrier substrate inside the application unit (10), to form a fired film containing microparticles; and a removal unit (30) which removes the microparticles from the fired film.

Description

Porous imide series resin film manufacture system, barrier film and porous imide series tree Adipose membrane manufacture method

Technical field

The present invention relates to porous imide series resin film manufacture system, barrier film and porous imide series resin film system Make method.

Background technology

Lithium ion battery is a kind of secondary cell, and it is formed as following structures：Positive pole in it impregnated in electrolyte and negative Barrier film is configured between pole, the direct electrical contact between positive pole and negative pole is prevented by barrier film.Lithium transition gold used in positive pole Category oxide, such as lithium, carbon (graphite) etc. used in negative pole.During charging, lithium ion is moved by barrier film from positive pole to negative pole, is put When electric, lithium ion is moved by barrier film from negative pole to positive pole.As such barrier film, use in recent years high and safe by heat resistance Property the barrier film that formed of high porosity polyimide film be known (for example, with reference to patent document 1 etc.).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-111470 publications

The content of the invention

The invention problem to be solved

Above-mentioned porous polyimide film is for example formed by following operations：Coating forms the polyamic acid comprising particulate Or polyimides does not burn till film, film is not burnt till to this and is burnt till and is formed and burn till film, from burning till remove in film particulate.Due to It was not present in a production line carrying out the manufacture system of above-mentioned 3 operations in the past, thus the manufacture of porous polyimide film Efficiency is not very high.Therefore, the higher system of manufacture efficiency is being sought.

In view of situation as above, it is an object of the invention to provide porous imide series resin film can be improved The porous imide series resin film manufacture system of manufacture efficiency, barrier film and porous imide series resin film manufacturing method.

Means for solving the problems

The porous imide series resin film manufacture system that the 1st aspect of the present invention is related to is manufacture porous acid imide The manufacture system of resin film, it includes following units：Coater unit, the coater unit will be sub- comprising polyamic acid, polyamides The liquid spreading of amine, polyamidoimide or polyamide and particulate is formed and does not burn till film in base material；Burn till unit, the burning The film that do not burn till peeled off from base material in coater unit or outside coater unit is burnt till into unit, so as to be formed comprising particulate Burn till film；And removing unit, the removing unit by particulate from burn till in film remove.

The barrier film that the 2nd aspect of the present invention is related to is the barrier film that formed using porous imide series resin film, porous Property imide series resin film is the porous imide series resin film manufacture system that is related to using the 1st aspect of the present invention and is made Into.

The porous imide series resin film manufacturing method that the 3rd aspect of the present invention is related to is manufacture porous acid imide The method of resin film, it includes following operations：Will comprising polyamic acid, polyimides, polyamidoimide or polyamide and The liquid spreading of particulate forms the operation for not burning till film after base material from base material stripping；Burnt till and shape to not burning till film Into the operation for burning till film comprising particulate；With by particulate from burn till in film remove operation.

The effect of invention

Mode of the invention, it is possible to increase the manufacture efficiency of porous imide series resin film.

Description of the drawings

[Fig. 1] is the figure of an example for illustrating the manufacture system that embodiments of the present invention are related to.

[Fig. 2] is the figure of an example for illustrating the nozzle arranged on coater unit of the present embodiment.

[Fig. 3] is the stereogram of an example for illustrating winder of the present embodiment.

[Fig. 4] is the stereogram for illustrating an example for burning till unit of the present embodiment.

[Fig. 5] is the stereogram of an example for illustrating removing unit of the present embodiment.

[Fig. 6] is the figure of an example of the manufacture process for illustrating imide series resin film of the present embodiment.

[Fig. 7] is the figure of an example for illustrating the manufacture system that variation is related to.

[Fig. 8] is the figure of an example for illustrating the manufacture system that variation is related to.

[Fig. 9] is the figure of an example for illustrating the manufacture system that variation is related to.

[Figure 10] is the figure of an example for illustrating the manufacture system that variation is related to.

[Figure 11] is the figure of an example for illustrating etch (etching) unit that variation is related to.

[Figure 12] is the figure of an example for illustrating the coiler device that variation is related to.

[Figure 13] is the figure of an example for illustrating the barrier film that embodiment is related to.

Specific embodiment

Hereinafter, embodiments of the present invention are illustrated referring to the drawings.Hereinafter, using XYZ coordinate system to the side in figure To illustrating.In the XYZ coordinate system, using with the plane of plane-parallel as X/Y plane.Will be parallel with the X/Y plane One hand designations is X-direction, is Y-direction by the hand designations orthogonal with X-direction.Additionally, by the direction orthogonal with X/Y plane It is denoted as Z-direction.Here explanation：To X-direction, Y-direction and Z-direction each for, the direction of arrow in figure is+direction, with arrow Direction in opposite direction is-direction.

Fig. 1 is the figure of an example for illustrating manufacture system SYS.Manufacture system SYS shown in Fig. 1 is manufacture porous tree The manufacture system of adipose membrane F (porous imide series resin film).Manufacture system SYS possesses：Coater unit 10, the coater unit The coating fluid of regulation is coated and is formed and do not burn till film FA by 10；Unit 20 is burnt till, the unit 20 pairs that burns till does not burn till film FA is burnt till, and so as to be formed film FB is burnt till；Removing unit 30, the removing unit 30 by particulate from burn till in film FB remove, So as to form porous resin film F；With control device (not shown), the control device plans as a whole the above-mentioned each unit of control.

Manufacture system SYS is for example configured to upper and lower 2 stratum, and coater unit 10 is configured in the 2nd layer segment, burns till unit 20 And removing unit 30 is configured in the 1st layer segment.Configuration within the same layer burn till unit 20 and removing unit 30 for example in the Y direction Upper configuration side by side, but this is not limited to, for example can also side by side match somebody with somebody on the compound direction of X-direction or X-direction with Y-direction Put.

It should be noted that configuration of each unit in the hierarchical structure, each layer with regard to manufacture system SYS etc., does not limit Due to aforesaid way, for example, by coater unit 10 and unit 20 can also be burnt till configure in the 2nd layer segment, removing unit 30 is matched somebody with somebody Put in the 1st layer segment.In addition it is also possible to all of unit is configured within the same layer.In this case, each unit can be configured For a row, it is also possible to configured with multiple row.Further, it is also possible to all of unit is configured in different stratum.

In manufacture system SYS, it is with banding formation not burn till film FA.(film FA is not burnt till in+Y the sides of coater unit 10 Conveying direction front), be provided with the winder 40 for not burning till film FA wound into rolls of banding.Burning till unit 20 - Y sides (not burning till the rear of the conveying direction of film FA), be provided with and web-like do not burnt till into film FA to burning till what unit 20 was sent Unloading part 50.In+Y the sides (burning till the front of the conveying direction of film FB) of removing unit 30, it is provided with F volume of porous resin film It is coiled into the winder 60 of web-like.

As described above, the interval of winder 60 is reached through burning till unit 20 and removing unit 30 from unloading part 50 In (the 1st layer segment), processed in so-called volume to volume (Roll-to-roll) mode.Therefore, in the interval, do not burn till Film FA, each film burnt till in film FB and porous resin film F are conveyed with continual state.

[coating fluid]

Here, before illustrating to each unit, the coating fluid of the raw material as porous resin film F is said It is bright.Resin material of the coating fluid comprising regulation, particulate and solvent.As the resin material of regulation, such as polyamide can be enumerated Acid, polyimides, polyamidoimide or polyamide.Used as solvent, can use can be by the organic of these resin material dissolvings Solvent.

In present embodiment, as coating fluid, can use 2 kinds of different coating fluids of particulate containing ratio (the first coating fluid and Second coating fluid).Specifically, it is prepared in the particulate containing ratio of the first coating fluid mode higher than the second coating fluid.By This, it is ensured that do not burn till film FA, burn till film FB and the intensity and flexibility of porous resin film F.Additionally, by arranging particulate The low layer of containing ratio, can realize the reduction of the manufacturing cost of porous resin film F.

For example, in the first coating fluid, resin material and particulate become 19 with volume ratio：81～45：65 mode is contained Have.Additionally, in the second coating fluid, resin material and particulate become 20 with volume ratio：80～50：50 mode is contained.But It is, so that the particulate containing ratio of the first coating fluid sets volume ratio higher than the mode of the particulate containing ratio of the second coating fluid.Need It is noted that with regard to the volume of each resin material, the value that can be multiplied by its proportion using the quality of each resin material and try to achieve.

In these cases, during using the cumulative volume of the first coating fluid as 100, if the volume of particulate is more than 65, grain Son is uniformly dispersed, if additionally, the volume of particulate be 81 within, particle disperses while aggegation does not occur each other yet.Therefore, it is possible to The adequate relief pore-forming in porous resin film F.If additionally, the volume ratio of particulate is within the range, being able to ensure that to not Burn till fissility when film FA carries out film forming.

During using the cumulative volume of the second coating fluid as 100, if the volume of particulate is more than 50, particulate monomer equably divides Dissipate, if additionally, the volume of particulate is within 80, particulate both will not aggegation each other, and also will not crack on surface, The porous resin film F good therefore, it is possible to be stably formed electrical characteristics.

2 kinds of above-mentioned coating fluids for example can be by advance disperseing fine-grained solvent and polyamic acid, polyimides, gathering Amide imide or polyamide are prepared so that arbitrary ratio is mixed.In addition it is also possible to disperse fine-grained molten in advance Polyamic acid, polyimides, polyamidoimide or polyamide are polymerized in agent and are prepared.For example, following sides can be passed through Formula is manufactured：Tetracarboxylic dianhydride and diamines are polymerized in fine-grained organic solvent is disperseed in advance and are formed polyamic acid, Or further carry out imidizate and form polyimides.

With regard to the viscosity of coating fluid, it is preferably set to be finally 300～2500cP, more preferably the scope of 400～1500cP, The more preferably scope of 600～1200cP.If the viscosity of coating fluid is within the range, film forming can be equably carried out.

For above-mentioned coating fluid, make and do not burn till film being dried to particulate and polyamic acid or polyimides In the case of FA, when the material of particulate is inorganic material hereinafter described, preferably become 2 with the ratio of particulate/polyimides The mode of～6 (mass ratioes) mixes particulate with polyamic acid or polyimides.More preferably 3～5 (mass ratioes).When micro- When the material of grain is organic material hereinafter described, preferably 1～3.5 (mass ratio) is become with the ratio of particulate/polyimides Mode mixes particulate with polyamic acid or polyimides.More preferably 1.2～3 (mass ratioes).Additionally, not burning making During film forming FA, by particulate and polyamic acid or poly- preferably in the way of the volume ratio of particulate/polyimides becomes 1.5～4.5 Acid imide mixes.More preferably 1.8～3 (volume ratios).Make do not burn till film FA when, if the matter of particulate/polyimides Amount ratio or the hole that volume ratio is the density that more than lower limit, then can obtain being suitable as barrier film, if below higher limit, then can Film forming is stably carried out in the case of enough the problems such as crackle in there is no viscosity increase, film.Replacing polyamic acid or polyamides Imines and make resin material in the case of polyamidoimide or polyamide, mass ratio is also same as described above.

Hereinafter, each resin material is specifically described.

For the polyamic acid used in present embodiment, use arbitrary tetracarboxylic acid with being not particularly limited Acid dianhydride be polymerized with diamines obtained from polyamic acid.The usage amount of tetracarboxylic dianhydride and diamines is not particularly limited, but relatively In 1 mole of tetracarboxylic dianhydride, 0.50～1.50 mole of diamines is preferably used, more preferably using 0.60～1.30 mole, especially Preferably use 0.70～1.20 mole.

Tetracarboxylic dianhydride can fit from the tetracarboxylic dianhydride for using as the synthesis material of polyamic acid all the time Preferably select.Tetracarboxylic dianhydride can be aromatic tetracarboxylic acid's dianhydride, or aliphatic tetracarboxylic dianhydride, but it is poly- from what is obtained From the viewpoint of the heat resistance of imide resin, aromatic tetracarboxylic acid's dianhydride is preferably used.Tetracarboxylic dianhydride can combine 2 kinds with Above use.

As the suitable concrete example of aromatic tetracarboxylic acid's dianhydride, pyromellitic acid anhydride, 1,1- double (2,3- bis- can be enumerated Carboxyl phenyl) ethane dianhydride, double (2,3- dicarboxyphenyis) methane dianhydrides, double (3,4- dicarboxyphenyis) methane dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, 2,2,6,6- bibenzene tetracarboxylic dianhydrides, 2,2- pair (3, 4- dicarboxyphenyis) propane dianhydride, double (2,3- dicarboxyphenyis) propane dianhydrides of 2,2-, 2,2- double (3,4- dicarboxyphenyis)- Double (2,3- the dicarboxyphenyis) -1,1,1,3,3,3- hexafluoropropane dianhydrides of 1,1,1,3,3,3- hexafluoropropane dianhydrides, 2,2-, 3, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, double (3,4- dicarboxyphenyis) ether dianhydrides, double (2,3- dicarboxyphenyis) ether dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 4,4- (to the epoxide of phenylene two) two O-phthalic acid dianhydrides, a 4,4- (sub- benzene The epoxide of base two) two O-phthalic acid dianhydrides, 1,2,5,6- naphthalenetetracarbacidic acidic dianhydrides, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- Naphthalenetetracarbacidic acidic dianhydride, 1,2,3,4- PMDAs, 3,4,9,10- perylene tetracarboxylic acid dianhydrides, 2,3,6,7- anthracene tetracarboxylic acid dianhydrides, 1,2,7,8- phenanthrene tetracarboxylic acid dianhydrides, the double phthalic anhydride fluorenes of 9,9-, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydride etc..As Aliphatic tetracarboxylic dianhydride, can enumerate such as ethylene-tetracarboxylic acid dianhydride, ethylene-dimalonic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, ring Hexane tetracarboxylic acid dianhydride, 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides, 1,2,3,4- cyclohexanetetracarboxylic acid dianhydrides etc..Wherein, from valency Lattice, the viewpoint such as easiness for obtaining consider, preferably 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and pyromellitic acid anhydride.Additionally, These tetracarboxylic dianhydrides both can be used alone or mix two or more and use.

Diamines can suitably be selected from the diamines for using as the synthesis material of polyamic acid all the time.Diamines can Think aromatic diamine, or aliphatic diamine, but from from the viewpoint of the heat resistance of the polyimide resin for obtaining, it is excellent Select aromatic diamine.These diamines can combine two or more and use.

As aromatic diamine, the diamino compounds of the phenyl for being bonded with 1 or 2～10 or so can be enumerated.Specifically For, it is phenylenediamine and its derivative, benzidine compound and its derivative, diamino-diphenyl compound and its derivative Thing, diaminourea triphenyl compound and its derivative, diaminourea naphthalene and its derivative, aminophenyiamino indane and its derivative Thing, diaminourea tetraphenyl compound and its derivative, diaminourea hexaphenyl compound and its derivative, Cardo type fluorenediamines spread out It is biological.

Phenylenediamine is m-phenylene diamine (MPD), p-phenylenediamine etc., as phenylenediamine derivative, to be bonded with the alkyl such as methyl, ethyl Diamines, such as 2,4- diaminotoluenes, 2,4- Sanyas phenylenediamine (2,4-triphenylenediamine) etc..

Benzidine compound is the compound that 2 aminophenyls are bonded with mutual phenyl.For example, it is 4, 4 '-benzidine, 4,4 '-diaminourea -2,2 '-bis- (trifluoromethyl) biphenyl etc..

Diamino-diphenyl compound is the chemical combination that mutual phenyl is bonded via other groups in 2 aminophenyls Thing.Key be ehter bond, sulphonyl key, thioether bond, based on the key of alkylidene or its deriveding group, imino group key, azo bond, phosphine oxide (phosphine oxide) key, amido link, ureylene (ureylene) key etc..It is 1～6 or so that alkylidene key is carbon number Alkylidene key, its deriveding group is the group that the hydrogen atom of more than 1 in alkylidene is replaced by halogen atom etc..

As the example of diamino-diphenyl compound, 3 can be enumerated, 3 '-diamino-diphenyl ether, 3,4 '-diaminourea two Phenyl ether, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino Base diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, Double (the p-aminophenyls of 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, 2,2- Base) propane, 2,2 '-bis- (p-aminophenyl) HFC-236fas, double (the p-aminophenyl) -1- amylenes of 4- methyl -2,4-, 4- methyl - It is double (p-aminophenyl) pentanes of double (the p-aminophenyl) -2- amylenes of 2,4-, imino-diacetic aniline, 4- methyl -2,4-, double (to ammonia Base phenyl) phosphine oxide, 4,4 '-chrysoidine, 4,4 '-diamino-diphenyl urea, 4,4 '-diamino-diphenyl acid amides, 1, Double (4- amino-benzene oxygens) benzene of 4-, double (4- amino-benzene oxygens) benzene of 1,3-, 1,3- double (3- amino-benzene oxygens) benzene, 4,4 '-bis- (4- Amino-benzene oxygen) biphenyl, double [4- (4- amino-benzene oxygens) phenyl] sulfones, double [4- (3- amino-benzene oxygens) phenyl] sulfones, 2,2- be double Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of [4- (4- amino-benzene oxygens) phenyl] propane, 2,2- etc..

Wherein, consider from viewpoints such as price, the easiness for obtaining, preferred p-phenylenediamine, m-phenylene diamine (MPD), 2,4- diaminourea first Benzene and 4,4 '-diamino-diphenyl ether.

Diaminourea triphenyl compound is 2 aminophenyls and 1 phenylene via other group bondings Compound, other groups may be selected and the same group being directed to described in diamino-diphenyl compound.As diaminourea three The example of phenyl compound, can enumerate double (m-aminophenyl epoxide) benzene of 1,3-, 1,3- double (p-aminophenyl epoxide) benzene, Isosorbide-5-Nitraes-bis- (p-aminophenyl epoxide) benzene etc..

As the example of diaminonaphthalene, 1,5-diaminonaphthalene and 2,6- diaminonaphthalene can be enumerated.

As the example of aminophenyiamino indane, 5- amino -1- (p-aminophenyl) -1,3,3- trimethyl indenes can be enumerated Full or 6- amino -1- (p-aminophenyl) -1,3,3- trimethyl indanes.

As the example of diaminourea tetraphenyl compound, can enumerate 4,4 '-bis- (p-aminophenyl epoxide) biphenyl, 2,2 '-it is bis- [4- (4 '-amino-benzene oxygen) phenyl] propane, 2,2 '-bis- [4- (4 '-amino-benzene oxygen) xenyl] propane, 2,2 '-it is bis- [right (m-aminophenyl epoxide) phenyl] benzophenone etc..

With regard to Cardo type fluorenediamine derivatives, 9,9- dianil fluorenes etc. can be enumerated.

Aliphatic diamine for example can be the aliphatic diamine that carbon number is 2～15 or so, specifically, can enumerate five Methylene diamine, hexamethylene diamine, heptamethylene diamines etc..

It should be noted that can also be these diamines hydrogen atom be selected from halogen atom, methyl, methoxyl group, cyano group, The compound that at least a kind substituent in the group of phenyl etc. replaces.

The means of the polyamic acid used in manufacture present embodiment are not particularly limited, it is, for example possible to use organic The known method such as method that acid, diamine component reacted is made in solvent.

Tetracarboxylic dianhydride is generally carried out in organic solvent with the reaction of diamines.For the reaction of tetracarboxylic dianhydride and diamines Used in organic solvent for, as long as can make tetracarboxylic dianhydride and two amine solvents and not with tetracarboxylic dianhydride and diamines The organic solvent of reaction, is not particularly limited.Organic solvent can be used alone or mix two or more and use.

The example of the organic solvent used in reaction as tetracarboxylic dianhydride and diamines, can enumerate N- methyl -2- pyrroles Alkanone, DMAC N,N' dimethyl acetamide, N, N- diethyl acetamides, N,N-dimethylformamide, N, N- DEFs, N- first Base caprolactam, N, N, N ', the nitrogenous polar solvent such as N '-tetramethylurea；Beta-propiolactone, gamma-butyrolacton, gamma-valerolactone, δ-penta The lactone such as lactone, γ-hexalactone, 6-caprolactone system polar solvent；Dimethyl sulfoxide (DMSO)；Acetonitrile；The fat such as ethyl lactate, butyl lactate Fat esters of gallic acid；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetic acid The ethers such as ester, ethyl cellosolve acetate；The phenol series solvent such as cresols class.These organic solvents can be used alone or mix 2 kinds Use above.The usage amount of organic solvent is not particularly limited, but preferably make the polyamic acid of generation content be 5～50 matter Amount %.

In these organic solvents, from from the viewpoint of the dissolubility of the polyamic acid for generating, preferred N- methyl -2- pyrrolidines Ketone, DMAC N,N' dimethyl acetamide, N, N- diethyl acetamides, N,N-dimethylformamide, N, N- DEFs, N- methyl Caprolactam, N, N, N ', the nitrogenous polar solvent such as N '-tetramethylurea.

Generally -10～120 DEG C, preferably 5～30 DEG C of polymerization temperature.Polymerization time is constituted not according to the raw material for using It is different together, but usually 3～24Hr (hour).Additionally, the organic solvent of the polyamic acid for obtaining in such a situa-tion is molten The intrinsic viscosity of liquid is preferably the scope of 1000～100,000 cP (centipoise), the scope of more preferably 5000～70,000 cP.

For the polyimides used in present embodiment, as long as can be dissolved in for the organic molten of coating fluid Soluble polyimide in agent, then do not limit its structure, molecular weight, it is possible to use known polyimides.With regard to poly- Acid imide, can have the functional group that can be condensed or the senses that can promote cross-linking reaction etc. when burning till such as carboxyl on side chain Group.

In order to form the polyimides for dissolving in organic solvent, using for importing on main chain the warp architecture of softness Monomer, for example, using ethylenediamine, hexamethylene diamine, Isosorbide-5-Nitrae-DACH, 1,3- DACHs, 4,4 '-diamino The aliphatic diamines such as base dicyclohexyl methyl hydride；2- methyl isophthalic acids, 4- phenylenediamines, o-tolidine, a tolidine, 3,3 '-diformazan The aromatic diamines such as epoxide benzidine, 4,4 '-diaminobenzene formailide；Polyethyleneoxide diamine, polypropyleneoxide diamine, polyoxy fourth The polyoxyalkylene diamines such as alkene diamines；Polysiloxane diamine；The double phthalic anhydrides of 2,3,3 ', 4 '-oxygen, 3,4,3 ', 4 '-oxygen are double adjacent Double (4- hydroxy phenyls) the propane dibenzoic acid ester groups -3,3 ' of phthalate anhydride, 2,2-, 4,4 '-tetracarboxylic acid dianhydride etc. is effective. Additionally, using with the monomer for improving deliquescent functional group in organic solvent, for example using 2,2 '-bis- (fluoroforms Base) -4,4 '-benzidine, 2- Trifluoromethyl-1s, the fluorinated diamine such as 4- phenylenediamines is also effective.Additionally, except above-mentioned use Beyond the deliquescent monomer for improving polyimides, can with the deliquescent scope of without prejudice to, and with it is above-mentioned<Polyamides Amino acid>Monomer identical monomer described in hurdle.

Used in the present invention, manufacture can be dissolved in the means of the polyimides in organic solvent without especially limit System, for example can be using following known methods：Chemical imidization is carried out for polyamic acid or add hot-imide, and make It is dissolved in method in organic solvent etc..As such polyimides, aliphatic polyimide (full aliphatic poly can be enumerated Acid imide), aromatic polyimide etc., optimization aromatic polyimides.Can be by with formula as aromatic polyimide (1) the polyamic acid Jing heat of the repetitive for representing or chemically ring-closure reaction and the material that obtains or will be with formula (2) table The polyimides of the repetitive for showing is dissolved in material obtained from solvent.In formula, Ar represents aryl.

For the polyamidoimide used in present embodiment, as long as having for coating fluid can be dissolved in Soluble polyamide acid imide in machine solvent, then do not limit its structure, molecular weight, it is possible to use known polyamide acyl Imines.With regard to polyamidoimide, can have functional group or can promote when burning till that carboxyl etc. can be condensed on side chain The functional group of cross-linking reaction etc..

Polyamidoimide used in present embodiment uses following substances with being not particularly limited：Make arbitrary Material obtained from trimellitic anhydride and di-isocyanate reaction, by by the reactive derivatives of arbitrary trimellitic anhydride with Precursor polymer carries out material obtained from imidizate obtained from the reaction of diamines.

As above-mentioned arbitrary trimellitic anhydride or its reactive derivatives, such as trimellitic anhydride, inclined benzene three can be enumerated The trimellitic anhydride halide such as acid anhydrides chloride, trimellitic anhydride ester etc..

As diisocyanate, can enumerate for example m-benzene diisocyanate, PPDI, 4,4 '-bis oxide (benzene Based isocyanate), 4,4 '-diisocyanate diphenyl methane, double [4- (4- isocyanates phenoxy groups) phenyl] sulfones, 2,2 '-it is bis- [4- (4- isocyanates phenoxy groups) phenyl] propane etc..

As diamines, can enumerate and the diamines identical diamines illustrated in the explanation of above-mentioned polyamic acid.

As polyamide, the polyamide for preferably being obtained by dicarboxylic acids and diamines, particularly preferred aromatic polyamide.

As dicarboxylic acids, maleic acid, fumaric acid, itaconic acid, citraconic acid, dimethyl maleic acid, phenyl horse can be enumerated Come sour, chloromaleic acid, dichloro- maleic acid, fluoro maleic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and connection Benzoic acid etc..

Next, illustrating to particulate.For particulate, can be little using such as rate of small round spheres height, particle diameter distribution index Particulate.Such particulate in a liquid dispersed excellent, becomes not the state of aggegation each other.It is (average as the particle diameter of particulate Diameter), for example, may be set to 100～2000nm or so.By using particulate as above, can make by follow-up The aperture that porous resin film F obtained from particulate is removed in operation is consistent.Therefore, it is possible to make to using porous resin film F The electric fields uniform that the barrier film of formation applies.

It should be noted that as the material of particulate, as long as it is insoluble in the solvent contained by coating fluid and follow-up Operation in the material that can remove from porous resin film F, then can be not particularly limited using known material.Example Such as, in inorganic material, silica (silica), titanium oxide, aluminum oxide (Al can be enumerated₂O₃) etc. metal oxide.Additionally, having In machine material, high molecular weight olefin (polypropylene, polyethylene etc.), polystyrene, epoxy resin, cellulose, polyethylene can be enumerated The organic polymer particulate such as alcohol, polyvinyl butyral resin, polyester, polymethyl methacrylate, polyethers.Additionally, as particulate One example, can enumerate (single dispersing) preparing spherical SiO 2 particles isocolloid silica, calcium carbonate etc..In this case, can Make the aperture of porous resin film F evenly.

Additionally, for the particulate included in the particulate included in the first coating fluid and the second coating fluid, rate of small round spheres, grain The all sizes such as footpath, material can be with identical, it is also possible to different from each other.Preferably, the particle diameter of the particulate for including in the first coating fluid Profile exponent is less or same than the particulate included in the second coating fluid.Or, it is preferable that include in the first coating fluid The rate of small round spheres of particulate is less or same than the particulate included in the second coating fluid.Moreover it is preferred that wrapping in the first coating fluid The particle phase included in the particulate for containing and the second coating fluid is less than the particle diameter (average diameter) of particulate, particularly preferably, first The particulate included in coating fluid is 100～1000nm (more preferably 100～600nm), and the particulate included in the second coating fluid is 500～2000nm (more preferably 700～2000nm).By the little grain of the particle diameter using the particulate than including in the second coating fluid Footpath as the particle diameter of the particulate included in the first coated film, the opening ratios in the hole on porous resin film F surfaces can be made high and Uniformly.Additionally, compared with the situation of the particle diameter of the particulate for making to be included in porous resin film F generally the first coating fluids, moreover it is possible to Enough improve film strength.

It should be noted that for above-mentioned coating fluid, except the resin material comprising regulation, particulate and solvent it Outward, the various additions such as releasing agent, dispersant, condensing agent, acid imide agent, surfactant can also as desired be included Agent.

[coater unit]

Coater unit 10 has delivery section 11, first jet 12, second nozzle 13, drying section 14 and stripping portion 15.

Delivery section 11 has conveying base material (base material) S, base material outlet roller 11a, backing roll 11b～11d, base material take-up roll 11e and outlet roller 11f.

Conveying base material S is with banding formation.Conveying base material S is sent from base material outlet roller 11a, with the side with tension force Formula is set up in backing roll 11b～11d, is wound using base material take-up roll 11e.As the material of conveying base material S, example can be enumerated Such as polyethylene terephthalate (PET), but it is not limited to this, or stainless steel and other metal materials.

Each roller 11a～11f is each abreast configured in X direction for example formed as cylindrical shape.It should be noted that each roller 11a～11f is not limited to configuration parallel in X direction, it is also possible to by least one roller with relative to the inclined mode of X-direction Configuration.For example, it is also possible to each roller 11a～11f is abreast configured along Z-direction, in the height and position identical mode in Z-direction Configuration.In this case, the state that conveying base material S will be erect with respect to the horizontal plane (X/Y plane) is moved along horizontal plane.

Base material outlet roller 11a is configured with being wound with the state of conveying base material S.Backing roll 11b is configured in base material and sends + Z the sides of roller 11a, and be configured in than base material outlet roller 11a more by-Y sides.Additionally, backing roll 11c is configured in backing roll + Z the sides of 11b, and be configured in than backing roll 11b more by+Y sides.By this 3 rollers (base material outlet roller 11a, backing roll 11b, 11c) configuration, convey base material S and supported by the face of-Y side ends comprising backing roll 11b.

Additionally, backing roll 11d is configured in the+Y sides of backing roll 11c, and it is configured in-Z the sides of backing roll 11c.Should In the case of, by the configuration of this 3 rollers of backing roll 11b～11d, convey faces of the base material S by the+Z side ends comprising backing roll 11c Supported.

It should be noted that also backing roll 11d can be configured in the height and position (position in Z-direction with backing roll 11c Put) roughly equal height and position.In this case, convey base material S be with the state almost parallel with X/Y plane along +Y direction from Backing roll 11c to backing roll 11d is conveyed.

Base material take-up roll 11e is configured in the-Z sides of backing roll 11d.Conveying base material S be along -Z direction from backing roll 11d to The conveying of base material take-up roll 11e.Outlet roller 11f is configured in the+Y sides and-Z sides of backing roll 11d.Outlet roller 11f will be using dry What dry portion 14 was formed does not burn till film FA along +Y direction conveying.This does not burn till film FA and is output roller 11f and exports to coater unit 10 It is outside.

It should be noted that above-mentioned roller 11a～11f is not limited to cylindrical shape, it is also possible to be formed with conical crown (crown).In this case, for the flexible correction of roller 11a～11f it is effective, conveying base material S or hereinafter described not Burning till film FA can equably contact with roller 11a～11f.Additionally, could be formed with the crown of radial pattern on roller 11a～11f. In this case, it is effective for preventing from conveying base material S or not burning till the complications of film FA.Additionally, on roller 11a～11f The crown (central portion in X-direction is with the part of bow) of matrix can also be formed with.In this case, can be along X side Conveyed to conveying base material S or not burning till film FA while tension force is given, therefore, it is for the generation for preventing fold Effectively.For following roller, it is also possible to be as described above the crown with pyramid type, radial pattern, matrix etc. Constitute.

Fig. 2 (a) is the stereogram of an example for illustrating first jet 12.As shown in Fig. 1 and Fig. 2 (a), first jet 12 The coated film (below, being designated as the first coated film F1) of the first coating fluid Q1 is formed on conveying base material S.First jet 12 has spray Go out the ejiction opening 12a of the first coating fluid Q1.In X-directions of the ejiction opening 12a with the size on such as length direction with conveying base material S The roughly the same mode of size and formed.

First jet 12 is configured in ejection position P1.Ejection position P1 is in the -Y direction relative to backing roll 11b Position.First jet 12 is arranged obliquely by ejiction opening 12a towards in the way of +Y direction.Therefore, ejiction opening 12a is towards conveying base The part that-Y the side ends for being supported by roller 11b in material S are supported.First jet 12 be directed to conveying base material S, in the horizontal direction from Ejiction opening 12a sprays the first coating fluid Q1.

Fig. 2 (b) is the stereogram of an example for illustrating second nozzle 13.As shown in Fig. 1 and Fig. 2 (b), second nozzle 13 The coated film for forming the second coating fluid Q2 in the mode Chong Die with the first coated film F1 on conveying base material S (below, is designated as second Coated film F2).Second nozzle 13 has the ejiction opening 13a for spraying the second coating fluid Q2.Ejiction opening 13a is with such as length direction Size and the roughly the same mode of size in the X-direction of conveying base material S and formed.

Second nozzle 13 is configured in ejection position P2.Ejection position P2 is in the +Z direction relative to backing roll 11c Position.Second nozzle 13 is configured by ejiction opening 13a towards in the way of -Z direction.Therefore, ejiction opening 13a directions conveying base material S In be supported by roller 11c+Z side ends support part.Second nozzle 13 is directed to conveying base material S, along gravity direction from spray Outlet 13a sprays the second coating fluid Q2.

It should be noted that first jet 12 and second nozzle 13 can be in X-direction, Y-direction and Z-directions What at least one side moved up.Additionally, also can by first jet 12 and second nozzle 13 be configured to around with X-direction Parallel axis rotation.Additionally, first jet 12 and second nozzle 13 also can be arranged in the following manner：Do not spraying coating fluid When, position of readiness (not shown) is configured in, when coating fluid is sprayed, from position of readiness above-mentioned ejection position is respectively moved to P1、P2.Additionally, may also set up the part of the prepared spray action for carrying out first jet 12 and second nozzle 13.

First jet 12 and second nozzle 13 (are not schemed respectively via connecting pipings (not shown) etc. with coating fluid supply source Show) connection.For first jet 12 and second nozzle 13, for example, can internally be provided with the coating fluid of holding ormal weight Maintaining part (not shown).In this case, during first jet 12 and second nozzle 13 can also have to being maintained at above-mentioned maintaining part Liquid body the temperature adjustment portion that is adjusted of temperature.

For painting output, first coated film F1 or second of each coating fluid sprayed from first jet 12 or second nozzle 13 The thickness of coated film F2, can be connected by each nozzle, each connecting pipings (not shown) or with coating fluid supply source (not shown) The pressure of pump (not shown), transporting velocity, distance of each nozzle location or conveying base material S and nozzle etc. being adjusted.The The thickness of one coated film F1 or the second coated film F2 is for example respectively 0.5 μm～500 μm.

It is excellent as in this embodiment using in the case of 2 kinds of coating fluids (the first coating fluid Q1 and the second coating fluid Q2) Choosing, adjusts the thickness of the first coated film F1 formed by the first coating fluid Q1 in the range of such as 0.5 μm～10 μm, The thickness of the second coated film F2 formed by the second coating fluid Q2 is for example adjusted in the range of 1 μm～50 μm.

It should be noted that between first jet 12 and second nozzle 13, can also be configured to make the first coated film The drying section (not shown) that F1 is dried.The drying section is preferably provided with heat drying portion.As heat drying portion, hot blast is preferably used Air supplying part, infrared heater.Heating-up temperature is such as 50 DEG C～150 DEG C of scope, preferably 50 DEG C～100 DEG C of scope. By forming the second coated film F2 after the first coated film F1 is dried, so as to for example suppress in the second coating fluid Particulate mix with the particulate in the first coated film F1.

As shown in figure 1, drying section 14 be configured in second nozzle 13 it is+Y sides, positioned at backing roll 11c and backing roll 11d Between position.Drying section 14 makes to coat two-layer coated film (the first coated film F1 and the second coated film on conveying base material S F2) it is dried, so as to be formed film FA is not burnt till.

Drying section 14 has chamber 14a and heating part 14b.Chamber 14a houses conveying base material S and heating part 14b.Heating part 14b is heated to first coated film F1 and the second coated film F2 of the formation on conveying base material S.As heating part 14b, can make With such as infrared heater etc..Heating part 14b is heated with 50 DEG C～100 DEG C or so of temperature to coated film.

Stripping portion 15 is will not burn till the part that film FA is peeled off from conveying base material S.In present embodiment, by operator's Manual operations is not limited to this not burnt till the stripping of film FA, it is also possible to using manipulator (manipulator) etc. Automatically carry out.The film FA that do not burn till peeled off from conveying base material S is exported to the outside of coater unit 10 using outlet roller 11f, And it is delivered to winder 40.It is wound using base material take-up roll 11e additionally, will peel off and do not burn till the conveying base material S after film FA.

[winder (1)]

Fig. 3 is the stereogram of the composition of+Y sides for schematically showing coater unit 10.

As shown in figure 3, in the+Y sides of coater unit 10, being provided with the delivery outlet 10b by film FA outputs are not burnt till.Will be from defeated The film FA that do not burn till of outlet 10b outputs is wound using winder 40.

Winder 40 is configured to be provided with shaft component SF in bearing 41.Shaft component SF will be exported not from delivery outlet 10b Burn till film FA to be wound and form rolled body R.Shaft component SF is arranged to be loaded and unloaded for bearing 41.Shaft component SF is pacified During loaded in bearing 41, its by can around parallel with X-direction axis rotation in the way of and supported.Winder 40 has The drive mechanism (not shown) for rotating the shaft component SF being installed in bearing 41.

It should be noted that in winder 40, not burn till film FA in the face of the first coated film F1 side be configured at outside Mode be wound to not burning till film FA.For example, shaft component SF is made to revolve along the counter clockwise direction of Fig. 1 by using drive mechanism Turn, so that do not burn till film FA being wound.By the way that shaft component SF is unloaded from bearing 41 with the state for defining rolled body R, So as to make rolled body R be moved to other units.

It should be noted that in figures 1 and 3, winder 40 is configured in the mode independent with coater unit 10, but not It is defined in this.For example, winder 40 also can be configured at the inside of coater unit 10.In this case, can not be in coater unit Delivery outlet 10b is configured in 10, and starts to be wound so as to shape to not burning till film FA from outlet roller 11f (or from backing roll 11d) Into rolled body R.

[unloading part]

Fig. 4 is the stereogram of the composition for schematically showing-Y sides for burning till unit 20.

As shown in figure 4, in the-Y sides for burning till unit 20, being provided with the input port 20a by film FA inputs are not burnt till.Unloading part 50 send for input port 20a and do not burn till film FA.

Unloading part 50 is configured to that shaft component SF can be installed in bearing 51.Shaft component SF can be installed on winder 40 Shaft component SF in bearing 41 is general.Therefore, it is possible to the shaft component unloaded from winder 40 SF to be installed on the axle of unloading part 50 Hold in 51.Thereby, it is possible to the rolled body R formed using winder 40 is configured at into unloading part 50.It should be noted that for For the bearing 41 of bearing 51 and winder 40, can be set as each apart from the highly equal of table top, it is also possible to be set in height The different position of degree.

When shaft component SF is installed in bearing 51, it is in the way of can be around the axis rotation parallel with X-direction And supported.Unloading part 50 has the drive mechanism (not shown) for rotating the shaft component SF being installed in bearing 51.By profit Shaft component SF being rotated clockwise along Fig. 1 is made with drive mechanism, so that constitute rolled body R does not burn till film FA to defeated Entrance 20a sends.It should be noted that due in above-mentioned winder 40, not burn till film FA in the first coated film F1 The face of side is configured at the mode in outside and is wound to not burning till film FA, therefore, pull out film FA will do not burnt till from rolled body R When, the first coated film F1 side will be configured in top.

[burning till unit]

In the present embodiment, it is to carry out the unit of high-temperature process to not burning till film FA to burn till unit 20.Burn till unit 20 Burn till to not burning till film FA, film FB is burnt till comprising particulate so as to be formed.Unit 20 is burnt till with chamber 21, heating part 22 With delivery section 23.Chamber 21 has the input port 20a that will do not burn till film FA inputs and will burn till the delivery outlet 20b that film FB is exported. Chamber 21 houses heating part 22 and delivery section 23.

What heating part 22 pairs was input into chamber 31 do not burn till film FA heats.Heating part 22 has in the Y direction simultaneously Multiple heater 22a of row configuration.As heater 22a, it is possible to use such as infrared heater etc..Heating part 22 throughout Configure to the scope of+Y side ends from the-Y side ends of the inside of chamber 21.Heating part 22 can be in the Y direction it is substantially overall In the range of heat to not burning till film FA.Heating part 22 can carry out adding in 120 DEG C～450 DEG C or so to not burning till film FA Heat.The heating-up temperature heated using heating part 22 according to the transporting velocity for not burning till film FA, the composition for not burning till film FA into Grade suitably to be adjusted.

Delivery section 23 has conveyer belt 23a, driven roller 23b, driven voller 23c and jockey pulley 23d, 23e.Conveyer belt 23a is Formed with endless, along Y-direction configuration.Conveyer belt 23a is that have durability using the firing temperature to not burning till film FA Material and formed.Conveyer belt 23a is set up in driven roller in the state of with tension force in the mode almost parallel with X/Y plane Between 23b and driven voller 23c.The state for not burning till film FA and burn till film FB to be placed on conveyer belt 23a is defeated along +Y direction Send.

Driven roller 23b is configured in the+Y side ends of the inside of chamber 21.Driven roller 23b for example formed as cylindrical shape, with X Direction abreast configures.Such as rotating driving device such as motor (motor) is provided with driven roller 23b.Driven roller 23b is arranged For：By the rotating driving device, can rotate around the axis parallel with X-direction.Rotated by driven roller 23b so that Conveyer belt 23a being rotated clockwise along Fig. 1.Rotated by conveyer belt 23a, so as to be placed on conveyer belt 23a not Burn till film FA and burn till film FB and convey along +Y direction.

Driven voller 23c is configured in the-Y side ends of the inside of chamber 21.Driven voller 23c for example formed as cylindrical shape, with X Direction abreast configures.Driven voller 23c to be formed with driven roller 23b identical diameter, with position (the height position in Z-direction Put) mode roughly equal with driven roller 23b configure.Driven voller 23c is configured to be revolved around the axis parallel with X-direction Turn.Driven voller 23c follows the rotation of conveyer belt 23a and rotates.

Jockey pulley 23d is configured in the+Z sides of driven voller 23c.Jockey pulley 23d is abreast configured with X-direction, and is set to Can rotate around X-axis.Jockey pulley 23d is configured to be moved up and down along Z-direction.Jockey pulley 23d can its with Clamp between driven voller 23c and do not burn till film FA.Jockey pulley 23d can be rotated with clamping the state for not burning till film FA.

Jockey pulley 23e is configured in the+Z sides of driven roller 23b.Jockey pulley 23e is abreast configured with X-direction, and is set to Can rotate around X-axis.Jockey pulley 23e is configured to be moved up and down along Z-direction.Jockey pulley 23e can its with Clamp between driven roller 23b and burn till film FB.Jockey pulley 23e can be rotated with clamping the state for burning till film FB.

Do not burnt till each clamping respectively between driven voller 23c and driven roller 23b by being formed as jockey pulley 23d, 23e Film FA and burn till the state of film FB, so as to it is continual do not burn till film FA and burn till nipped 2 positions in film FB it Between part in, will be weakened from outside tension force.Thereby, it is possible to prevent from applying excessive to not burning till film FA and burning till film FB Load.Jockey pulley 23d, 23e can be adjusted such that not to being configured at not burning till film FA and burn till in chamber 21 Film FB applies tension force.

[removing unit]

Removing unit 30 has chamber 31, etch portion 32, cleaning part 33, drying section 34 and delivery section 35.Chamber 31 has The input port 30a and the delivery outlet 30b by porous resin film F outputs of film FB inputs will be burnt till.Chamber 31 houses etch portion 32nd, cleaning part 33, drying section 34 and delivery section 35.

32 pairs, etch portion burns till film FB and carries out etch, the particulate removing included in film FB will be burnt till, so as to form porous Resin film F.In etch portion 32, by will burn till film FB impregnated in can by particle dissolution or the etching solution of decomposition so as to remove Particulate.The supply unit (not shown) of etching solution as supply is provided with etch portion 32, the storage unit of etching solution can be stored.

Cleaning part 33 is cleaned to the porous resin film F after etch.Cleaning part 33 is configured in the+Y in etch portion 32 Side (front of the conveying direction of porous resin film F).Cleaning part 33 has the supply unit (not shown) of supply cleaning fluid.This Outward, there can also be the recoverer (not shown) reclaimed to the waste liquid after cleaning porous resin film F, carry out porous tree Discharge opeing portion (not shown) of the discharge opeing of adipose membrane F etc..

Porous resin film F after 34 pairs of cleanings of drying section is dried.Drying section 34 is configured in the+Y of cleaning part 33 Side (front of the conveying direction of porous resin film F).Be provided with drying section 34 porous resin film F is heated plus Hot portion etc..

Delivery section 35 is conveyed and burns till film FB and porous resin film F through etch portion 32, cleaning part 33 and drying section 34. Delivery section 35 has conveyer belt 35a, driven roller 35b and driven voller 35c.It should be noted that except driven roller 35b and driven voller Beyond 35c, can be with the backing roll of the inside of etch portion 32, cleaning part 33, drying section 34 configuration support belt 35a.

Conveyer belt 35a is with endless formation, along Y-direction configuration.Conveyer belt 35a is to use to have above-mentioned etching solution The material of durability and formed.Conveyer belt 35a is set up in the state of with tension force in the mode almost parallel with X/Y plane Between driven roller 35b and driven voller 35c.Burn till film FB and porous resin film F is placed on conveyer belt 35a.

Driven roller 35b is configured in the+Y side ends of the inside of chamber 31.Driven roller 35b for example formed as cylindrical shape, with X Direction abreast configures.The rotating driving devices such as such as motor are provided with driven roller 35b.Driven roller 35b is set to：Pass through The rotating driving device, can rotate around the axis parallel with X-direction.Rotated by driven roller 35b so that conveyer belt 35a being rotated clockwise along Fig. 1.Rotated by conveyer belt 35a, so as to be placed on conveyer belt 35a film FB is burnt till And porous resin film F is conveyed along +Y direction.

Driven voller 35c is configured in the-Y side ends of the inside of chamber 31.Driven voller 35c for example formed as cylindrical shape, with X Direction abreast configures.Driven voller 35c to be formed with driven roller 35b identical diameter, with position (the height position in Z-direction Put) mode roughly equal with driven roller 35b configure.Driven voller 35c is configured to be revolved around the axis parallel with X-direction Turn.Driven voller 35c follows the rotation of conveyer belt 35a and rotates.

It should be noted that for removing unit 30, being not limited to situation about removing particulate by etch. For example, using the organic material that can decompose at lower temperatures compared with polyimides as the material of particulate in the case of, Can be by being heated so that particulate breakup to burning till film FB.As such organic material, as long as and polyimides The organic material that can decompose at lower temperatures is compared, is then used with being not particularly limited.For example, can enumerate by linearly gathering The resin particle that compound, known depolymerization polymer are formed.The molecule of common linear polymer polymer in thermal decomposition Chain can randomly be cut off, and depolymerization polymer is the polymer that polymer resolves into monomer in thermal decomposition.Both of which passes through Decomposing to becomes low-molecular weight or CO₂And disappear from burning till in film FB.The decomposition temperature of particulate in this case is preferably 200 ～320 DEG C, more preferably 230～260 DEG C.If decomposition temperature is more than 200 DEG C, even if the higher boiling used in coating fluid Also film forming can be carried out in the case of solvent, the selecting range for burning till the firing condition in unit 20 broadens.If additionally, decomposing temperature Degree is less than 320 DEG C, then can not only make particulate disappear with imposing fire damage to burning till film FB.

[winder (2)]

Fig. 5 is the stereogram of the composition of+Y sides for schematically showing removing unit 30.

As shown in figure 5, in the+Y sides of removing unit 30, being provided with the delivery outlet 30b for exporting porous resin film F.Will It is wound using winder 60 from the porous resin film F of delivery outlet 30b outputs.

Winder 60 is configured to be provided with shaft component SF in bearing 61.Shaft component SF is more by what is exported from delivery outlet 30b Permeability resin film F winds and forms rolled body RF.Shaft component SF is arranged to be loaded and unloaded for bearing 61.Shaft component SF is pacified During loaded on bearing 61, its by can around parallel with X-direction axis rotation in the way of and supported.Winder 60 has to be made The drive mechanism (not shown) of the shaft component SF rotations being installed in bearing 61.Shaft component SF is revolved by using drive mechanism Turn, so that porous resin film F is wound.By the way that shaft component SF is unloaded from bearing 61 with the state for defining rolled body RF Under such that it is able to reclaim rolled body RF.

[manufacture method]

Next, one of the running to manufacturing porous resin film F using manufacture system SYS constructed as disclosed above Individual example is illustrated.Fig. 6 (a)～(f) is the figure of an example of the manufacture process for illustrating porous resin film F.

First, formed in coater unit 10 and do not burn till film FA.In coater unit 10, rotate base material outlet roller 11a And conveying base material S is sent, by conveying base material S lodges after backing roll 11b～11d, it is wound using base material take-up roll 11e. Then, start to send conveying base material S successively from base material outlet roller 11a, while being wound using base material take-up roll 11e.

In this condition, first jet 12 is made to be configured at first position P1, by ejiction opening 12a towards +Y direction.Thus, make Ejiction opening 12a is supported by the part of roller 11b supports towards in conveying base material S.Then, the first coating fluid Q1 is made from ejiction opening 12a Spray.First coating fluid Q1 is sprayed from ejiction opening 12a to +Y direction, after reaching conveying base material S, with the shifting of conveying base material S Move and coat on conveying base material S.Thus, as shown in Fig. 6 (a), form what is formed by the first coating fluid Q1 on conveying base material S First coated film F1.In the first coated film F1, particles A 2 is contained with the volume ratio for specifying in resin material A1.

Then, second nozzle 12 is made to be configured at second place P2, by ejiction opening 13a towards -Z direction.Thus, ejiction opening is made 13a is supported by the part of roller 11c supports towards in conveying base material S.Then, the second coating fluid Q2 is made to spray from ejiction opening 13a.Will Second coating fluid Q2 sprays from ejiction opening 13a to -Z direction, after arrival is formed in the first coated film F1 on conveying base material S, Moving and coating in the first coated film F1 with conveying base material S.Thus, as shown in Fig. 6 (b), in the first coated film F1 The second coated film F2 that formation is formed by the second coating fluid.Volume in the second coated film F2, in resin material A1 to specify Than containing particles A 2.It should be noted that for particulate containing ratio, being set as the first coated film F1 compared with the second coated film F2 Greatly.

It should be noted that due to ejiction opening 12a, 13a are being supported by into roller 11b, 11c support towards in conveying base material S Part in the state of be coated with the first coating fluid Q1 and the second coating fluid Q2, thus in the first coating fluid Q1 and the second coating fluid Q2 When reaching conveying base material S, the power for acting on conveying base material S is born by backing roll 11b, 11c.Therefore, it is possible to suppress to convey base material S Generation flexure, vibration etc., can be stably formed the first coated film F1 and the second coating on conveying base material S with uniform thickness Film F2.

Then, base material S movements are conveyed and the laminated portions of the first coated film F1 and the second coated film F2 is input into drying When in the chamber 14a in portion 14, the drying of the first coated film F1 and the second coated film F2 is carried out in drying section 14.Drying section 14 In, using heating part 14b, the first coated film F1 and the second coated film F2 are carried out with such as 50 DEG C～100 DEG C or so of temperature Heating.If the temperature range, then can not produce in the case of warpage, deformation etc. to the first coated film in conveying base material S F1 and the second coated film F2 are heated.It is dried by the duplexer to the first coated film F1 and the second coated film F2, from And define as shown in Fig. 6 (c) and do not burn till film FA.

It should be noted that in this specification, so-called duplexer is referred to comprising above-mentioned first coated film F1 and above-mentioned second Coated film F2 does not burn till film.When forming porous imide series resin film according to the present invention, in first liquid and the second liquid In the case of using the homogenous resins in polyamic acid, polyimides, polyamidoimide or polyamide in body respectively, comprising shape Into above-mentioned first coated film F1 and above-mentioned second coated film F2 do not burn till film (or porous imide series resin film) although Be essentially 1 layer, but due to define particulate containing ratio it is different do not burn till film (or with many of the different region of porosity Permeability imide series resin film), therefore in this manual, will be including homogenous resins used in first liquid and second liquid Situation be referred to as duplexer in interior situation.

Then, base material S movements are conveyed, when the fore-end for not burning till film FA reaches backing roll 11d (stripping portion 15), is passed through The manual operations of such as operator, the fore-end is peeled off from conveying base material S.In present embodiment, due to as conveying base The materials'use of material S is such as PET, therefore is formed and do not burn till film being dried the first coated film F1 and the second coated film F2 During FA, become easily to peel off from conveying base material S, thus operator can easily be peeled off.

After the fore-end for not burning till film FA is peeled off, conveying base material S is continued to move to, and using first jet 12 first is formed Coated film F1.Additionally, continuing with second nozzle 13 forms the second coated film F2, and formed using drying section 14 and do not burn till film FA.Thus, formed with banding and do not burn till film FA, the length for not burning till film FA exported from drying section 14 to+Y sides is progressively longer. Operator persistently peels off to not burning till film FA in stripping portion 15.Then, the front end for not burning till film FA being stripped is changed into During the length of the shaft component SF for reaching winder 40, operator will not burn till film FA lodges in outlet roller by manual operations 11f, while the fore-end for not burning till film FA is attached to into shaft component SF.Then, sequentially form and quilt with not burning till film FA Peel off, in winder 40 rotate shaft component SF.Thus, by peel off do not burn till film FA successively from coater unit 10 it is defeated Go out, and the shaft component SF using winder 40 is wound and forms rolled body R.As shown in Fig. 6 (d), rolled body R is constituted not It is the state peeled off from conveying base material S to burn till film FA, and surface and the back side are exposed simultaneously.

It should be noted that for the operation for peeling off the fore-end for not burning till film FA and the fore-end that will be peeled off For being attached to operation of shaft component SF etc., however it is not limited to which operator for example also can make by way of manual operations is carried out Automatically carried out with manipulator etc..Additionally, in order to improve the fissility for not burning till film FA, it is also possible in advance conveying base material S's Surface forms release layer.

By the length of regulation do not burn till film FA on shaft component SF after, film FA cut-outs will not burnt till, while by axle Component SF is unloaded together with rolled body R from bearing 41.Then, new shaft component SF is installed on the bearing 41 of winder 40, The end that cuts for not burning till film FA is attached to shaft component SF and rotates it, is continuously formed and is not burnt till film FA, thus, it is possible to Make new rolled body R.

On the other hand, such as operator will be delivered to together with the shaft component SF that rolled body R is unloaded from bearing 41 and send Go out portion 50, and be installed on bearing 51.The conveying action of shaft component SF and installation action can also use manipulator, conveying device Deng automatically carrying out.Shaft component SF is installed on after bearing 51, film FA will not be burnt till from web-like by rotating shaft component SF Pull out successively in body R, and film FA will not burnt till and be input into burning till in the chamber 21 of unit 20.It should be noted that will not burn When the front end of film forming FA is input into chamber 21, can be carried out by operator's manual operations, it is also possible to using manipulator etc. certainly Carry out dynamicly.

Input is placed on conveyer belt 23a to the film FA that do not burn till in chamber 21, with the rotation of conveyer belt 23a to +Y direction is conveyed.It should be noted that can be adjusted to tension force using jockey pulley 23d, 23e.Then, do not burn till in conveying Film FA is not burnt till while film FA using heating part 22 pairs to burn till.

Temperature when burning till is different and different according to the structure for not burning till film FA, preferably 120 DEG C～375 DEG C or so, More preferably 150 DEG C～350 DEG C.Additionally, in the particle comprising in the case of organic material, it is necessary to be set as than its thermal decomposition temperature Degree lower temperature.It should be noted that in the case where coating fluid includes polyamic acid, preferably completing it in this burns till Imidization, but do not burn till film FA and be made up of polyimides, polyamidoimide or polyamide, do not burnt till using burning till unit 20 pairs The situation that film FA carries out high-temperature process is not subject to the limits.

Additionally, for firing condition, for example, in the case where coating fluid is comprising polyamic acid and/or polyimides, Can adopt and keep the method for 20 minutes to after 375 DEG C, in 375 DEG C Jing 3 hours from room temperature, or following institute can be carried out The interim heating stated：375 DEG C (each step is kept for 20 minutes) are periodically warming up to from room temperature with 50 DEG C of amplitude, most finally 375 DEG C are kept for 20 minutes etc..In addition it is also possible to the end for not burning till film FA is fixed in template of SUS etc. so as to prevent Deformation.

Burnt till by such, so as to define as shown in Fig. 6 (e) film FB is burnt till.In film FB is burnt till, in Jing acyls The inside of the resin bed A3 of imidization or high-temperature process includes particles A 2.The thickness for burning till film FB can be by using such as micrometer Deng the thickness for determining multiple positions and average and try to achieve.As preferred average film thickness, in the case of for barrier film etc., Preferably 3 μm～500 μm, more preferably 5 μm～100 μm, more preferably 10 μm～30 μm.

Film FB is burnt till for what is formed in unit 20 is burnt till, it is if exporting from burning till in unit 20, it is not rolled Be input into removing unit 30.It should be noted that when the fore-end for burning till film FB is input into removing unit 30, can be with Carried out by operator's manual operations, it is also possible to automatically carried out using manipulator etc..

Input to the film FB that burns till of removing unit 30 is placed on conveyer belt 35a, with the rotation of conveyer belt 35a to +Y direction is conveyed.In removing unit 30, with the conveying for burning till film FB, removing for particles A 2 is carried out in etch portion 32 first Go.As particles A 2 material use such as silica in the case of, will burn till in etch portion 32 film FB impregnated in it is low dense In the etching solutions such as the aqueous hydrogen fluoride solution of degree.Thus, particles A 2 is dissolved in etching solution and is removed, such as shown in Fig. 6 (f), shape Into in porous resin film F of the inside of resin bed A3 comprising porous portion A4.

Then, with the rotation of conveyer belt 35a, porous resin film F is sequentially input to cleaning part 33 and drying section 34 In.In cleaning part 33, porous resin film F is cleaned using cleaning fluid, and carry out discharge opeing.Additionally, in drying section 34 In, the porous resin film F after discharge opeing is heated, remove cleaning fluid.Then, by porous resin film F from removing unit Export in 30, be wound using the shaft component SF of winder 60.

As it was noted above, because manufacture system SYS of the present embodiment is included：Coater unit 10, it will be comprising poly- The resin material A1 of amic acid, polyimides, polyamidoimide or polyamide and coating fluid (first coating fluid of particles A 2 Q1 and the second coating fluid Q2) coat conveying base material S and formed and do not burn till film FA；Unit 20 is burnt till, it is in the coater unit The film FA that do not burn till peeled off from conveying base material S in 10 is burnt till, and film FB is burnt till comprising particulate so as to be formed；And removing unit 30, its by particles A 2 from burn till in film FB remove, therefore, it is possible to the formation of film FA not being burnt till with a set of flow process, not being burnt till Film FA's burns till (formation for burning till film FB) and the removing of particles A 2 (formation of porous resin film F) this 3 operations.Thus, The manufacture efficiency of porous resin film F can be improved.

Further, since coater unit (10) form banding on base material (conveying base material S) do not burn till film (FA), therefore can Suitable for the manufacturing process of volume to volume mode etc., porous imide series resin film (porous resin film can be efficiently formed F)。

Additionally, for removing unit (20), due to will using burn till unit (10) burn till obtained by burn till film (FB) Do not introduce and remove particulate (A2) successively not rolledly, carry out well from the work burnt till to particulate removing therefore, it is possible to efficiency Sequence.

Further, since possess the film (FA) that do not burn till that will be peeled off from base material (conveying base material S) and being wound and forming web-like The winder (40) of body (R), therefore, it is possible to easily carry out the conveying between unit.

Additionally, rolled body (R) is the feelings of the rolled body for not burning till film (FA) of the banding peeled off from base material (conveying base material S) Under condition, pull out successively and burnt till from rolled body due to burning till unit (10) film will not burnt till, therefore, it is possible to efficient landform Into burning till film FB.

Further, since using (the first coating of the containing ratio of at least particulate (A2) first liquid different from each other as liquid Liquid Q1) and second liquid (the second coating fluid Q2), and first liquid and second liquid are coated by base by coater unit (10) Material (conveying base material S) do not burn till film (FA) with what the different mode of at least particulate containing ratio was laminated so as to be formed, therefore, The porous imide series resin film (porous resin film F) formed based on film will not be burnt till by this is used as the situation of barrier film Under, ion can be moved successfully, also, with only with the first coating fluid Q1 formed same porosity porous imide series tree The situation of adipose membrane is compared, and is more able to ensure that as film strength.

Additionally, for the manufacture method of porous resin film F of the present embodiment, because it includes：Will bag (first applies the coating fluid of the resin material A1 containing polyamic acid, polyimides, polyamidoimide or polyamide and particles A 2 Cloth liquid Q1 and the second coating fluid Q2) coat conveying base material S after, peel off from conveying base material S and form the operation of not burning till film FA； Burn till to not burning till film FA, so as to form the operation for burning till film FB comprising particles A 2；With by particles A 2 from burning till film FB The operation of middle removing, (film is burnt till therefore, it is possible to the formation of film FA is not burnt till with a set of flow process, burning till for film FA is not burnt till The formation of FB) and particles A 2 removing (formation of porous resin film F) this 3 operations.Thereby, it is possible to improve porous tree The manufacture efficiency of adipose membrane F.

Further, since not burning till film (FA) is formed with banding, therefore it is applicable to the manufacture work of volume to volume mode etc. Sequence, can be efficiently formed porous imide series resin film (porous resin film F).

Further, since by will burn till film (FB) it is not rolled be introduced into successively and particulate (A2) removed from burning till in film Go, carry out well from the operation burnt till to particulate removing therefore, it is possible to efficiency.

Further, since the film (FA) that do not burn till that will be peeled off from base material (conveying base material S) is wound and forms rolled body (R), therefore, it is possible to easily carrying out the conveying between unit.

Additionally, rolled body is the feelings of the rolled body (R) for not burning till film (FA) of the banding peeled off from base material (conveying base material S) Under condition, pull out successively and burnt till from rolled body due to film will do not burnt till, therefore, it is possible to be efficiently formed film FB is burnt till.

Further, since using (the first coating of the containing ratio of at least particulate (A2) first liquid different from each other as liquid Liquid Q1) and second liquid (the second coating fluid Q2), and by the way that first liquid and second liquid are coated into base material (conveying base material S) Do not burn till film (FA) with what the different mode of the containing ratio of at least particulate (A2) was laminated so as to be formed, therefore, it is possible to manufacture Ion can successfully be moved and can ensure that (many as the porous imide series resin film of film strength when as barrier film Permeability resin film F).

[variation]

Although in the above-described embodiment, enumerating in coater unit 10 and burning till and be configured between unit 20 winder 40 It is illustrated as a example by composition, but is not limited to this.Fig. 7 is the part for illustrating manufacture system SYS2 that variation is related to Example figure.

For example, as shown in fig. 7, winder 40 can be not provided with, and it is configured to not burning for exporting from coater unit 10 Film forming FA is input into burning till in unit 20.In this case, burn till unit 20 by from coater unit 10 export, via relaying roller 70 and convey the film FA that do not burn till introduce successively and burnt till, burn till film FB so as to be formed.

As described above, burn till unit (20) will from base material (conveying base material S) peel off not burn till film (FA) not rolled Introduce successively and burnt till, therefore, it is possible to continuously never burnt till film FA formation to the formation of film FB is burnt till Operation.

In addition, although in the above-described embodiment, enumerating will not in the stripping portion 15 being arranged inside coater unit 10 Burn till as a example by the composition that film FA is peeled off from conveying base material S and be illustrated, but be not limited to this.For example, it is also possible to apply Film FA and conveying base material S will not be burnt till in cloth unit 10 does not carry out integrated winding not strippedly, in the outside of coater unit 10 Film FA will not burnt till while impregnated in liquid to peel off from conveying base material S.Fig. 8 is to illustrate the manufacture system that variation is related to The figure of the example of a part of SYS3.

For example, as shown in figure 8, coater unit 10 has not burning till film FA and convey base material S does not carry out one not strippedly The winder 73 of bodyization winding.Winder 73 has bearing 16 and shaft component SF2.Bearing 16 is configured in the-Z of backing roll 11d Side.Shaft component SF2 is arranged to be loaded and unloaded for bearing 16.When shaft component SF2 is installed in bearing 16, it is can enclose Supported around the mode of the axis rotation parallel with X-direction.Being provided with coater unit 10 makes to be installed in bearing 16 The drive mechanism (not shown) of shaft component SF2 rotations.Shaft component SF2 is rotated by using the drive mechanism, thus will not burnt Film forming FA and conveying base material S carry out integrated winding, so as to form rolled body RS.

The outside of coater unit 10 is provided with bearing 71.- Z the sides of the bearing 71 are provided with dipping portion 72.Dipping portion 72 have container 72a, the liquid 72b being contained in container 72a and the roller 72c being dipped in liquid 72b.As liquid 72b, for example, can enumerate water etc..

Using shaft component SF2 to do not burn till film FA and conveying base material S and carry out integrated winding and when forming rolled body RS, it is first First shaft component SF2 is unloaded from bearing 16.Then, shaft component SF2 is installed on the bearing 71 being arranged on outside coater unit 10.

Shaft component SF2 is installed on after bearing 71, film FA will not burnt till and conveying base material S is pulled out and soaked from rolled body RS Stain is in liquid 72b.For example so that do not burn till the duplexer lodge of film FA and conveying base material S in the downside of roller 72c.The situation Under, not burning till film FA and conveying base material S for pulling out from rolled body RS impregnated in successively in liquid 72b.For example, operator is not Burn till and will not burn till film FA from the S strippings of conveying base material in the state of film FA and conveying base material S impregnated in liquid 72b.

As noted previously, as possess and being wound the film (FA) that do not burn till comprising base material (conveying base material S) and forming volume The winder (73) of shape body (RS), therefore, it is possible to easily carry out the conveying between unit.Additionally, rolled body is comprising base material In the case of the rolled body (RS) for not burning till film (FA) of the banding of (conveying base material S), due to possessing base material from rolled body The dipping portion (72) that film is peeled off from the base material, therefore energy are impregnated in the liquid (liquid 72b) of regulation and will not burnt till after pull-out It is enough stably to be peeled off.

Additionally, impregnated in mode in liquid 72b as making not burn till film FA, it is not limited to not burn till film FA from defeated The situation for sending base material S to peel off.For example, it is also possible to the film FA that do not burn till peeled off from conveying base material S impregnated in the liquid such as water.Figure 9 is the figure of the example for the part for illustrating manufacture system SYS4 that variation is related to.

As shown in figure 9, being provided with the second dipping portion 74 in the+Y sides of coater unit 10.Second dipping portion 74 has container 74a, the liquid 74b being contained in container 74a and the roller 74c being dipped in liquid 74b.Export from coater unit 10 Do not burn till film FA to impregnated in liquid 74b via roller 74c.In this case, can make not burn till film FA and impregnate in liquid 74b Such as 10 seconds～5 minutes or so, preferably 30 seconds～40 seconds or so.Thereby, it is possible to suppress burnt till to not burning till film FA When form fold.

Make from conveying base material S peel off when not burning till film FA and impregnated in the liquid such as water, can after impregnating using winding Do not burn till film FA and be wound in 40 pairs, portion, it is also possible to after impregnating without winder 40.

Additionally, making after film FA impregnated in the liquid such as water, can to have and not burn this from not burning till of peeling off of conveying base material S The operation that film forming FA is pressurizeed.As the means pressurizeed, can enumerate and the operation that film FA is pressed is not burnt till to this.By This, can suppress be dried or form fold when burning till to not burning till film FA.

It should be noted that after the dipping for not burning till film FA without winder 40 in the case of, will via relaying roller And the film FA that do not burn till for conveying is introduced successively and burnt till, so as to be formed film FB is burnt till.Thus, will due to burning till unit (20) From base material (conveying base material S) peel off do not burn till film (FA) it is not rolled introduce successively and burnt till, therefore, it is possible to continuous Never burnt till the operation of the formation to the formation of film FB is burnt till of film FA.By it is above-mentioned conveyed do not burn till film FA Introducing is burnt till before unit, the operation that the liquid adhered to when can arrange to dipping is dried or absorbs water.

Additionally, in addition to the composition of above-mentioned embodiment, the porous to being formed by removing unit 30 can also be arranged The post-processing unit that resin film F is post-processed.Figure 10 is an example for illustrating manufacture system SYS5 that variation is related to Figure.

As shown in Figure 10, post-processing unit 80 is configured between removing unit 30 and winder 60.As the post processing Unit 80, it is possible to use the antistatic unit 81 of process is for example de-energized to porous resin film F.Take in antistatic unit 81 It is loaded with such as neutralizer such as electro-dissociator (Ionizer).

As noted previously, as the film (porous resin film F) that burns till possessed to eliminating particulate (A2) is carried out at antistatic The antistatic unit (81) of reason, therefore, it is possible to remove electrostatic in the porous resin film F after removing from particulate.

Additionally, as post-processing unit 80, it is possible to use the etch list for for example removing a part of porous resin film F Unit 82.Figure 11 (a) is the figure of an example for schematically showing etch unit 82.As shown in Figure 11 (a), etch unit 82 has There is the resettlement section 82a for containing treatment fluid 82b.As treatment fluid 82b, it is possible to use such as aqueous slkali etc..By by porous Resin film F impregnated in treatment fluid 82b with the stipulated time, so as to as shown in Figure 11 (b), the inside of porous portion A4 is removed Go.In this case, the burr of porous portion A4 are removed, and connectedness is guaranteed.

Using etch unit 82 as post-processing unit 80 in the case of, carrying out post processing using etch unit 82 Afterwards, can further carry out porous resin film F drying process or after toast treatment process.Drying process or rear baking are processed The temperature of operation suitably sets, for example, 100～300 DEG C according to the species of the resin of porous resin film F.

Using etch unit 82 as post-processing unit 80 in the case of, can be in the drying section in above-mentioned removing unit 30 Discharge opeing is carried out in 34, is not dried or plus thermally porous resin film F is delivered in etch unit 82.In this case, exist In discharge opeing in drying section 34, the liquid that will attach on the porous resin film F after cleaning is removed.It is preferred that in drying section 34 Suction roll etc. is provided with, is contacted with porous resin film F by making suction roll such that it is able to conveying porous resin film F's The liquid being attached on porous resin film F is absorbed simultaneously.

As noted previously, as comprising the part removing for burning till film (porous resin film F) that will eliminate particulate (A2) Etch unit (82), therefore the inner face of porous portion A4 included in porous resin film F becomes smooth, and the company of being able to ensure that The general character.

In addition, although in above-mentioned embodiment, as winder 40,60, enumerating makes shaft component SF enter in bearing 41,61 It is illustrated as a example by the composition that luggage is unloaded, but is not limited to this, for example, winding as shown in figure 12 can also be used to fill Put 90.Hereinafter, enumerate in case of replacing winder 40 using coiler device 90 to illustrate.

As shown in figure 12, coiler device 90 have framework 91, shaft component SF, bearing 92, drive division 93, relaying roller 94a～ 94e and roller support 95.Support shaft member SF of framework 91, bearing 92, drive division 93, relaying roller 94a～94e, roller support 95 Each several part.

The film FA that do not burn till exported from coater unit 10 is wound and forms rolled body R by shaft component SF.Shaft component SF is arranged to be loaded and unloaded for bearing 92.When shaft component SF is installed in bearing 92, it is with can be around flat with X-direction The mode of capable axis rotation and supported by bearing 92.By defining the state of rolled body R by shaft component SF from bearing 92 Unload such that it is able to which rolled body R is moved or is recycled in other units.

Relaying roller 94a～94e will not burn till film FA and be delivered to shaft component SF while adjusting and not burning till the tension force of film FA. Relaying roller 94a～94e is each abreast configured for example formed as cylindrical shape with X-direction.In present embodiment, film FA is not burnt till Set up according to the order of relaying roller 94a, 94b, 94c, 94d, 94e, but be not limited to this, it is also possible to do not use in a part After roller.It should be noted that at least one in relaying roller 94a～94e can also be enable to move by roller support 95. For example, roller support 95 can be enable to relay roller 94b move along Z-direction or Y-direction.In addition it is also possible to be configured to pass through Roller support 95 makes relaying roller 94b rotate around the axis AX parallel with X-axis.In this case, moved by making relaying roller 94b The amount (distance) of (rotation) is fed back in the winding speed of bearing 92 such that it is able to make the tension force for not burning till film FA keep constant. In addition it is also possible to for following compositions：Make the moveable weight-Y sides, configuring via fulcrum for being located at relaying roller 94b It is (not shown) mobile, so as to change to relaying the load that roller 94b applies.In this case, adjust right by using above-mentioned weight The load that relaying roller 94b applies such that it is able to which the tension force of film FA is not burnt till in regulation.

For relaying roller 94a～94e, however it is not limited to abreast configure with X-direction, it is also possible to incline relative to X-direction Tiltedly configure.Additionally, relaying roller R21～R25 is not limited to cylindrical shape, it is also possible to using being formed with pyramid type, radial pattern, matrix etc. Crown relaying roller.

It should be noted that above-mentioned coiler device 90 can also replace winder 60 and use.Additionally, by making axle structure Part SF to do not burn till the films such as film FA with winding when contrary direction rotate, can not will burn till the films such as film FA and send.Therefore, also may be used To replace unloading part as escribed above 50 using coiler device 90.

[barrier film]

Next, the barrier film 100 being related to embodiment is illustrated.Figure 13 is illustrate lithium ion battery 200 one The ideograph of example, it is illustrated that the state that a part is cut open.As shown in figure 13, lithium ion battery 200 has and has concurrently just The metal shell 201 and negative terminal 202 of extreme son.Metal shell 201 be internally provided with positive pole 201a, negative pole 202a, With barrier film 100, they impregnated in electrolyte (not shown).Barrier film 100 is configured between positive pole 201a and negative pole 202a, is prevented The only electrical contact between positive pole 201a and negative pole 202a.As positive pole 201a, using lithium transition-metal oxide, as negative pole 202a, uses such as lithium, carbon (graphite) etc..

Porous resin film F described in above-mentioned embodiment can be used as the barrier film 100 of the lithium ion battery 200. In this case, by make for example to be formed with the face of the first coated film F1 for lithium ion battery negative pole 202a sides such that it is able to carry High battery performance.It should be noted that, although carrying out as a example by the barrier film 100 of the lithium ion battery 200 of square is enumerated in Figure 13 Illustrate, but be not limited to this.Above-mentioned porous resin film F is in any type of lithium ion battery such as cylinder type, laminated-type Barrier film in can use.It should be noted that in addition to the barrier film of lithium ion battery, above-mentioned porous resin film F is also Can as the separation film of electrolyte film in fuel cell, gas or liquid, advanced low-k materials and use.

More than, embodiment is illustrated, but the present invention is not limited to description above, and can be not Various changes are carried out in the range of the purport for departing from the present invention.

For example, although in above-mentioned embodiment and variation, enumerate and come using 2 kinds of different coating fluids of particulate containing ratio It is illustrated in case of film FA is not burnt till in formation, but is not limited to this, it is also possible to is formed not using a kind of coating fluid Burn till film.In this case, first jet 12 and any one party in second nozzle 13 can not be used, it is also possible to by a nozzle Save.In the case that one nozzle is saved, preferably first jet 12 is saved and second nozzle 13 is used.

In addition, although in above-mentioned embodiment and variation, enumerate using burn till unit 20 formed burn till after film FB, will Burn till the composition that film FB is not input into into removing unit 30 not rolledly as a example by and be illustrated, but be not limited to this, Can be will to burn till the mode that film FB is wound.In this case, it is possible to use the coiler device 90 illustrated in above-mentioned variation.

In addition, although in above-mentioned embodiment and variation, coater unit 10 is enumerated, unit 20 is burnt till and is removed single It is illustrated as a example by the composition of each configuration 1 of unit 30, but is not limited to this.For example, it is also possible to by said units At least one unit is set to multiple stage.In this case, by treatable in such as time per unit will not burn till film FA, burn till Component (such as length etc.) few unit of film FB or porous resin film F configures more such that it is able to improve manufacture system SYS overall manufacture efficiency.

In addition, although in above-mentioned embodiment and variation, enumerate coater unit 10, burn till unit 20, removing unit 30 and post-processing unit 80 (antistatic unit 81, etch unit 82) in each unit will not burn till film FA, burn till film FB or many Each film in permeability resin film F is illustrated in case of the Y-direction conveying, but is not limited to this.For example, can be with Make arbitrary unit by film in X direction, Y-direction, Z-direction or the conveying of their compound direction, it is also possible to it is suitable in 1 unit Change conveying direction.

In addition, although in above-mentioned embodiment and variation, enumerate be coated in unit 10 coating, burn till unit It is illustrated in case of removing this 3 operations in burning till in 20, removing unit 30, but is not limited to this. For example, in the case of the materials'use polyimides as coated film, polyamidoimide or polyamide, can not carry out Burn till.Therefore, in the case where not burnt till, for example, by burning till between unit 20 and removing unit 30 arrange winding dress Put and carrying device etc. such that it is able to do not burn till film FA in the way of without unit 20 is burnt till by what is formed in coater unit 10 It is input into into removing unit 30.Additionally, in the case of not burnt till, manufacturing the manufacture system of porous imide series resin film It can be the manufacture system comprising following units：Coater unit, the coater unit will be comprising polyamic acid, polyimides, poly- The liquid spreading of amide imide or polyamide and particulate is formed and does not burn till film in base material；And removing unit, the removing list Unit from the coater unit or the coater unit it is outer from the base material peel off described in do not burn till remove in film it is described micro- Grain.It should be noted that in the case where not burnt till, by porous resin film F from the removing unit 30 for removing particulate After output, above-mentioned rear baking treatment process can be carried out.Before rear baking treatment process, can be through post-processing unit 80 And/or etch unit 82.

In addition, although in above-mentioned embodiment and variation, enumerate and porous is formed by so-called volume to volume mode It is illustrated as a example by the composition of resin film F, but is not limited to this.For example, after the process in removing unit 30 terminates In the case that porous resin film F is exported from removing unit 30, winder 60 can not be utilized to be wound, but to advise Fixed length cut-out, and reclaim the film after cut-out.

Description of reference numerals

SYS, SYS2, SYS3, SYS4, SYS5 ... manufacture system (porous imide series resin manufacture system) F ... porous Property resin film (porous imide series resin film) FA ... do not burn till film FB ... burn till film S ... conveying base material (base material) Q1 ... First coating fluid F1 ... the first coated film Q2 ... the second coating fluid F2 ... the second coated film A1 ... resin material A2 ... particulates R, RS, RF ... rolled body 10 ... coater unit 12 ... first jet 13 ... second nozzle 14 ... drying section 15 ... stripping portion 20 ... burn till unit 30 ..., and winder 72 ... dipping portion 80 ... the post processing of removing unit 32 ... etch portion 40,60,73 ... is single Unit 81 ... antistatic unit 82 ... etch unit 90 ... coiler device 100 ... barrier film 200 ... lithium ion battery

Claims

1. porous imide series resin film manufacture system, it is the manufacture system for manufacturing porous imide series resin film, institute Manufacture system is stated comprising following units：

Coater unit, the coater unit will be comprising polyamic acid, polyimides, polyamidoimide or polyamide and particulate Liquid spreading formed and do not burn till film in base material；

Burn till unit, the unit that burns till is in the coater unit or the outer institute peeled off from the base material of the coater unit State and do not burn till film and burnt till, film is burnt till comprising the particulate so as to be formed；With

Removing unit, the removing unit removes the particulate from described burning till in film.

2. porous imide series resin film manufacture system as claimed in claim 1, wherein, the coater unit is in the base The described of banding is formed on material and does not burn till film.

3. porous imide series resin film manufacture system as claimed in claim 1 or 2, wherein, the removing unit is by institute State and burn till film and do not introduce and remove the particulate successively not rolledly, the film that burns till is burnt till unit and burnt till using described 's.

4. the porous imide series resin film manufacture system as any one of claims 1 to 3, it possesses winder, The winder will be wound from film is not burnt till described in base material stripping or comprising film is not burnt till described in the base material And form rolled body.

5. porous imide series resin film manufacture system as claimed in claim 4, wherein, it is from described in the rolled body It is described to burn till unit by the film that do not burn till from described in the case of the rolled body for not burning till film of the banding that base material is peeled off Pull out successively in rolled body and burnt till.

6. porous imide series resin film manufacture system as claimed in claim 4, it possesses dipping portion, in the rolled body Be the banding comprising the base material the rolled body for not burning till film in the case of, the dipping portion is by the base material from described During the liquid of regulation is pulled out and impregnated in rolled body, and the film that do not burn till is peeled off from the base material.

7. the porous imide series resin film manufacture system as any one of claims 1 to 3, wherein, it is described to burn till Unit will from the base material peel off described in do not burn till film it is not rolled introduce successively and burnt till.

8. the porous imide series resin film manufacture system as any one of claim 1～7, it includes antistatic list Unit, the antistatic unit is burnt till film and carries out antistatic process to eliminating described in the particulate.

9. the porous imide series resin film manufacture system as any one of claim 1～8, it includes etch list Unit, the etch unit will eliminate the part removing that film is burnt till described in the particulate.

10. the porous imide series resin film manufacture system as any one of claim 1～9, wherein, as described Liquid, using at least particulate containing ratio first liquid different from each other and second liquid,

The coater unit by the way that the first liquid and the second liquid are coated into the base material, so as to be formed with least What the different mode of particulate containing ratio was laminated described does not burn till film.

11. barrier films, it is the barrier film formed using porous polyimide film, and the porous polyimide film is to utilize right Require 1～10 any one of porous imide series resin film manufacture system and made by.

12. porous imide series resin film manufacturing methods, its be manufacture porous imide series resin film method, the side Method includes following operations：

By the liquid spreading comprising polyamic acid, polyimides, polyamidoimide or polyamide and particulate after base material, from The base material is peeled off and forms the operation of not burning till film；

The film that do not burn till is burnt till and formed the operation for burning till film comprising the particulate；With

By the particulate from the operation burnt till and removed in film.

13. porous imide series resin film manufacturing methods as claimed in claim 12, wherein, the film that do not burn till is with band What shape was formed.

The 14. porous imide series resin film manufacturing methods as described in claim 12 or 13, wherein, by burning till described Film is introduced successively not rolledly, so as to the particulate be removed from described burning till in film.

The 15. porous imide series resin film manufacturing methods as any one of claim 12～14, wherein, will be from institute State the described of base material stripping not burning till film or be wound and form rolled body comprising film is not burnt till described in the base material.

16. porous imide series resin film manufacturing methods as claimed in claim 15, wherein, it is from institute in the rolled body State base material stripping the banding the rolled body for not burning till film in the case of, by it is described do not burn till film from the rolled body according to Secondary pull-out is simultaneously burnt till.

17. porous imide series resin film manufacturing methods as claimed in claim 15, wherein, the rolled body be comprising In the case of the rolled body for not burning till film of the banding of the base material, the base material is pulled out and soaked from the rolled body Stain peels off the film that do not burn till from the base material in the liquid of regulation.

The 18. porous imide series resin film manufacturing methods as any one of claim 12～14, wherein, will be from institute The film that do not burn till for stating base material stripping is not introduced successively and burnt till not rolledly.

The 19. porous imide series resin film manufacturing methods as any one of claim 12～18, wherein, to removing The described of the particulate burns till film and carries out antistatic process.

The 20. porous imide series resin film manufacturing methods as any one of claim 12～19, wherein, will remove The part removing for burning till film of the particulate.

The 21. porous imide series resin film manufacturing methods as any one of claim 12～20, wherein, as institute Liquid is stated, using at least particulate containing ratio first liquid different from each other and second liquid,

By the way that the first liquid and the second liquid are coated into the base material, so as to be formed with least particulate containing ratio not With mode be laminated described do not burn till film.